CN110643068B - Metal phenylphosphonate flame-retardant material with adjustable morphology, preparation method and application thereof - Google Patents
Metal phenylphosphonate flame-retardant material with adjustable morphology, preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 77
- 239000002184 metal Substances 0.000 title claims abstract description 77
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 description 58
- 229920000647 polyepoxide Polymers 0.000 description 58
- 239000004677 Nylon Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- 229920001778 nylon Polymers 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000002861 polymer material Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000008187 granular material Substances 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- LYFQZBRXUFXPSD-UHFFFAOYSA-H cerium(3+) dioxido-oxo-phenyl-lambda5-phosphane Chemical class [Ce+3].[Ce+3].[O-]P([O-])(=O)c1ccccc1.[O-]P([O-])(=O)c1ccccc1.[O-]P([O-])(=O)c1ccccc1 LYFQZBRXUFXPSD-UHFFFAOYSA-H 0.000 description 3
- WNVHHKBEWRPOHX-UHFFFAOYSA-L cobalt(2+);dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [Co+2].[O-]P([O-])(=O)C1=CC=CC=C1 WNVHHKBEWRPOHX-UHFFFAOYSA-L 0.000 description 3
- DRNJFFYTADAYNB-UHFFFAOYSA-H dialuminum;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [Al+3].[Al+3].[O-]P([O-])(=O)C1=CC=CC=C1.[O-]P([O-])(=O)C1=CC=CC=C1.[O-]P([O-])(=O)C1=CC=CC=C1 DRNJFFYTADAYNB-UHFFFAOYSA-H 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitrogen-phosphorus-silicon metal compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/00—Use of ingredients characterised by shape
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a metal phenylphosphonate flame retardant material with adjustable morphology, a preparation method and application thereof. The graphene has a shielding and blocking effect, and the metal phenylphosphonate material has good catalytic carbonization performance. The synergistic effect of the two greatly improves the flame retardant property of the high molecular material. The flame retardant has good thermal stability and flame retardant property, and the preparation method is simple and feasible, and has wide application prospect in the field of high-molecular flame retardant.
Description
Technical Field
The invention belongs to the field of high-molecular flame retardance, and particularly relates to a metal phenylphosphonate flame-retardant material with adjustable morphology, a preparation method and application thereof.
Background
The polymer material has good mechanical, physical and chemical properties and corrosion resistance, and can be widely applied to the fields of communication, electronics, medical treatment, chemical industry, aerospace and the like. However, most of high polymer materials are easy to burn, have great fire hazard, and greatly limit the practical application of the high polymer materials, so that the flame retardant modification of the high polymer materials becomes an important means for widening the application field of the high polymer materials. Flame retardants can be classified into halogen-based, organic phosphorus-based, nitrogen-based, silicon-based, and nitrogen-phosphorus-silicon metal compounds, etc., depending on the flame retardant element. The phosphorus flame retardant has the advantages of high efficiency, environmental protection and the like, but has the problems of low thermal stability, easy hydrolysis and the like. The metal phenyl phosphonate flame retardant has the advantages of hydrolysis resistance, high thermal stability and the like, is concerned by people and becomes a research hotspot in the field of flame retardance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a metal phenylphosphonate flame-retardant material with adjustable morphology, a preparation method and application thereof, and solves the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows: the metal phenylphosphonate flame-retardant material with adjustable morphology is provided, and the structural formula of the flame-retardant material is shown as the following formula:
wherein M isn+Is Ce3+、Al3+、Zn2+Or Co2+。
The metal phenylphosphonate flame-retardant material disclosed by the invention comprises the sheet-shaped and rod-shaped appearances; when the coordinated metal ion is Ce3+、Al3+When the flame-retardant material is in a sheet-layer shape, the metal phenylphosphonate flame-retardant material is prepared by the following steps of (1) preparing a flame-retardant material; when the coordinated metal ion is Zn2+、Co2+When the flame-retardant material is used, the flame-retardant material is in a rod shape.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the metal phenylphosphonate flame retardant material with the adjustable morphology is provided, piperazine is reacted with graphene oxide to obtain piperazine reduction modified graphene oxide, and phenylphosphonic acid is coordinated with metal ions and reacted with the modified graphene oxide to obtain the metal phenylphosphonate flame retardant material; wherein the metal ion is Ce3+、Al3+、Zn2+Or Co2+The shape of the metal phenylphosphonate flame-retardant material is adjusted by changing metal ions; the synthetic route is shown in figure 5.
The preparation method of the metal phenylphosphonate flame-retardant material with the adjustable morphology specifically comprises the following steps:
(1) adding graphene oxide and water into a reaction container, performing ultrasonic treatment at room temperature for 1h, stirring for 1-4 h, adding piperazine into the container, and adding N2Condensing and refluxing for 4-8 h at 80-120 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 50-100 ℃ to obtain piperazine reduction modified graphene oxide (Pip-G)O)；
In a preferred embodiment of the present invention, the mass ratio of the graphene oxide to the water to the piperazine is 1: 0.2-0.8: 1-5;
(2) adding phenylphosphonic acid, water and Pip-GO into a reaction container, stirring for 20-40 min, then adding metal salt, stirring for 20-40 min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 18-30 h at 80-120 ℃, centrifugally washing with ethanol, and drying in vacuum at 50-100 ℃ to obtain the metal phenylphosphonate flame retardant material (MHPP-PG);
in a preferred embodiment of the present invention, the metal salt is one of cerium nitrate, aluminum nitrate, zinc acetate and cobalt acetate.
In a preferred embodiment of the present invention, the mass ratio of the phenylphosphonic acid to the water to the Pip-GO is 1: 0.05-0.15: 1 to 2
In a preferred embodiment of the present invention, the molar ratio of phenylphosphonic acid to metal salt is 1: 1.5 to 2.5.
The third technical scheme adopted by the invention for solving the technical problems is as follows: the application of the metal phenylphosphonate flame-retardant material with the adjustable morphology in polymer preparation materials is provided, and the preparation method comprises the step of preparing the flame-retardant composite material which is prepared by taking epoxy resin and PA as carriers and adding the metal phenylphosphonate flame-retardant material.
In a preferred embodiment of the present invention, a flame retardant composite material comprises a polymer material, the above metal phenylphosphonate flame retardant material and a curing agent; the flame-retardant metal phenylphosphonate material is mixed with a high polymer material to prepare a corresponding flame-retardant composite material, wherein the flame-retardant metal phenylphosphonate material accounts for 1-10 wt% of the high polymer material.
The high polymer material is thermosetting E51 bisphenol A epoxy resin (EP) and thermoplastic NC010 nylon resin (PA); the curing agent is 4, 4-diaminodiphenylmethane (DDM); the mass ratio of the high polymer material to the curing agent is 3-5: 1.
the preparation method of the thermosetting flame-retardant epoxy resin flame-retardant composite material comprises the following steps: and (2) adding a metal phenyl phosphonate flame-retardant material and a solvent into the epoxy resin prepolymer at the temperature of 60-140 ℃, stirring until the mixture is transparent, pumping until no bubbles are generated, adding the curing agent, completely dissolving, and sequentially curing at the temperature of 110-130 ℃ for 1-5 h, at the temperature of 130-150 ℃ for 2-4 h, and at the temperature of 170-190 ℃ for 2-4 h to obtain the thermosetting flame-retardant epoxy resin flame-retardant composite material. The solvent is one of acetone, chloroform and dichloromethane.
The preparation method of the thermoplastic flame-retardant nylon resin flame-retardant composite material comprises the following steps: and (3) taking the thermoplastic nylon resin and the metal phenylphosphonate flame-retardant material, drying in a vacuum oven at 60-120 ℃, and putting in a double-screw extruder according to a certain proportion for melt blending. The temperature of 3 sections of the extruder is set to be 210-230 ℃, 220-230 ℃ and 220-230 ℃ respectively. And cooling the blend, cutting into granules, drying the granules in a drying box, and performing injection molding by using an injection molding machine to obtain a standard sample so as to obtain the thermoplastic flame-retardant nylon resin flame-retardant composite material.
The invention has the beneficial effects that:
(1) the metal phenyl phosphonate flame retardant material can obtain metal phenyl phosphonate flame retardant materials with two structures by changing metal ions coordinated with phenyl phosphonic acid, wherein the metal phenyl phosphonate obtained by coordination of trivalent metal is a two-dimensional extended lamellar structure, and the metal phenyl phosphonate obtained by coordination of divalent metal is a rod-shaped structure; the experimental result shows that the two flame retardants are excellent respectively, the sheet-shaped metal phenylphosphonate material has better flame retardant property, and the rod-shaped metal phenylphosphonate material has better mechanical property and can be selected according to the requirements of practical application;
(2) the reduced graphene in the metal phenylphosphonate flame-retardant material has a shielding and blocking effect, and is cooperated with the metal phenylphosphonate to flame-retardant a high polymer material, and the corresponding high polymer material has the advantages of high thermal stability and good flame retardant property;
(3) the metal phenyl phosphonate contains benzene rings, can form pi-pi bonds with graphene, and effectively inhibits aggregation and stacking of the graphene, so that the shielding effect of the graphene is further improved.
(3) The metal phenyl phosphonate contains phosphorus elements, has high-efficiency flame retardant performance similar to that of phosphorus flame retardants, contains metal ions compared with the phosphorus flame retardants, has the advantages of catalytic carbonization and the like, and can efficiently improve the flame retardant performance of high polymer materials when applied to the high polymer materials.
Drawings
FIG. 1 SEM spectra of series of four metal phenylphosphonates obtained in examples 1-4; wherein, (A, A ', E, E') is the cerium phenylphosphonate series of example 1, (B, B ', F, F') is the aluminum phenylphosphonate series of example 2, (C, C ', G, G') is the cobalt phenylphosphonate series of example 3, and (D, D ', H, H') is the zinc phenylphosphonate series of example 4.
FIG. 2 XRD patterns of four series of metal phenylphosphonate samples obtained in examples 1-4; wherein (A) is cerium phenylphosphonate series of example 1, (B) is aluminum phenylphosphonate series of example 2, (C) is cobalt phenylphosphonate series of example 3, and (D) is zinc phenylphosphonate series of example 4.
FIG. 3 (A-B) Heat Release curves, (C-D) Smoke Release curves for CeHPP-PG/EP obtained in examples 21 to 24.
FIG. 4 dynamic thermomechanical analysis (DMA) curves for CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP, and ZnHPP-PG/EP obtained in examples 21-24.
FIG. 5 is a synthesis route diagram of a metal phenylphosphonate flame retardant material with controllable morphology.
Detailed Description
Examples 1 to 4
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide (Pip-GO).
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 0.632g of Pip-GO into four reaction containers, stirring for 30min, respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, respectively pouring the reaction solution into four tetrafluoroethylene reaction kettles, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and vacuum drying at 60 ℃ to obtain four metal phenylphosphonate flame retardant materials (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
The morphology of the four metal phenylphosphonate flame-retardant materials was observed by using a thermal field emission scanning electron microscope, and the measurement results are shown in fig. 1.
The phase structure of the metal phenylphosphonate flame-retardant material is measured by an X-ray diffractometer, and the measured result is shown in FIG. 2.
Examples 5 to 8
Preparing flame-retardant epoxy resin:
respectively weighing 20g of four epoxy resin prepolymers, heating to 80 ℃, respectively adding 0.25g (1 wt%) of the cerium phenylphosphonate, aluminum phenylphosphonate, zinc phenylphosphonate and cobalt phenylphosphonate flame-retardant materials of examples 1-4 and 30mL of chloroform into the four epoxy resin prepolymers, ultrasonically stirring until the materials are transparent, exhausting until no bubbles are generated, respectively adding 5g of a curing agent 4, 4-diaminodiphenylmethane (DDM) until the materials are completely dissolved, then pouring the mixture into a preheated mold, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 3h and 180 ℃ for 2h to obtain four flame-retardant epoxy resins (CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnPG/EP).
And taking the obtained flame-retardant epoxy resin for oxygen index test. The oxygen indices of CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP were determined to be 26.9%, 26.5%, 25.2% and 25.4% respectively according to GB/T2406-2009.
Examples 9 to 12
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide (Pip-GO).
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 1.264g of Pip-GO into four reaction containers, stirring for 30min, then respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, pouring the reaction solution into four tetrafluoroethylene reaction kettles, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and vacuum drying at 60 ℃ to obtain four metal phenylphosphonate flame retardant materials (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
Examples 13 to 16
Preparing flame-retardant epoxy resin:
respectively weighing 20g of four epoxy resin prepolymers, heating to 80 ℃, respectively adding 0.77g (3 wt%) of the metal phenyl phosphonate flame-retardant material of example 9-12 and 30mL of chloroform into the four epoxy resin prepolymers, ultrasonically stirring until the materials are transparent, exhausting until no bubbles are generated, respectively adding 5g of curing agent 4, 4-diaminodiphenylmethane (DDM) until the materials are completely dissolved, then pouring the materials into a preheated mold, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 3h and 180 ℃ for 2h to obtain four flame-retardant epoxy resins (CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP).
And taking the obtained flame-retardant epoxy resin for oxygen index test. The oxygen indices of CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP were respectively 29.1%, 28.9%, 28.3% and 28.1% according to GB/T2406-2009.
Examples 17 to 20
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide (Pip-GO).
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 0.632g of Pip-GO into four reaction containers, stirring for 30min, then respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, pouring the reaction solution into four tetrafluoroethylene reaction kettles, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and vacuum drying at 60 ℃ to obtain four metal phenylphosphonate flame retardant materials (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
Examples 21 to 24
Preparing flame-retardant epoxy resin:
respectively weighing 20g of four epoxy resin prepolymers, heating to 80 ℃, respectively adding 1.31g (5 wt%) of the metal phenyl phosphonate flame-retardant material of example 17-20 and 30mL of dichloromethane into the four epoxy resin prepolymers, ultrasonically stirring until the materials are transparent, exhausting until no bubbles are generated, respectively adding 5g of a curing agent 4, 4-diaminodiphenylmethane (DDM) until the materials are completely dissolved, then pouring the materials into a preheated mold, and sequentially curing at 120 ℃ for 4h, 140 ℃ for 3h and 180 ℃ for 2h to obtain four flame-retardant epoxy resins (CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP).
The CeHPP-PG/EP thus obtained was subjected to cone calorimetry, and the heat release and smoke release curves are shown in FIG. 3.
The obtained CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP were subjected to dynamic thermomechanical analysis (DMA) and three-point bending test, and the results are shown in FIG. 4 and Table 1.
And taking the obtained flame-retardant epoxy resin for oxygen index test. According to GB/T2406-2009, the oxygen indexes of CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP are respectively 33.6%, 33.2%, 31.9% and 31.7%.
Table 1 shows the data of dynamic thermomechanical analysis (DMA) and three-point bending test of CeHPP-PG/EP, AlHPP-PG/EP, CoHPP-PG/EP and ZnHPP-PG/EP obtained in examples 21 to 24.
TABLE 1
Examples 25 to 28
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide(Pip-GO)。
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 1.264g of Pip-GO into four reaction containers, stirring for 30min, then respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, pouring the reaction solution into four tetrafluoroethylene reaction kettles, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and vacuum drying at 60 ℃ to obtain four metal phenylphosphonate flame retardant materials (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
Examples 29 to 32
Preparing flame-retardant nylon resin:
four parts of 20g of nylon resin were weighed, 0.2g (1 wt%) of the metal phenylphosphonate flame retardant material of examples 25-28 was added to each of the four parts of nylon resin, dried in a vacuum oven at 80 ℃ and melt blended in a twin screw extruder. The temperatures of the 3 sections of the extruder are set to be 220 ℃, 225 ℃ and 230 ℃ respectively. And (3) cooling the blend, cutting into granules, drying the granules in a drying box at 60 ℃, and performing injection molding by using an injection molding machine to obtain four flame-retardant nylon resins (CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA).
And taking the obtained flame-retardant nylon resin for oxygen index test. The oxygen indices of CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA were determined to be 26.0%, 25.8%, 24.9% and 24.7% respectively according to GB/T2406-2009.
Examples 33 to 36
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide (Pip-GO).
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 0.948g of Pip-GO into four reaction containers, stirring for 30min, then respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and drying in vacuum at 60 ℃ to obtain the metal phenylphosphonate flame retardant material (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
Examples 37 to 40
Preparing flame-retardant nylon resin:
four parts of 20g of nylon resin were weighed, 0.62g (3 wt%) of the metal phenylphosphonate flame retardant material of examples 33-36 was added to each of the four parts of nylon resin, dried in a vacuum oven at 80 ℃ and melt-blended in a twin-screw extruder. The temperatures of the 3 sections of the extruder are set to be 220 ℃, 225 ℃ and 230 ℃ respectively. And (3) cooling the blend, cutting into granules, drying the granules in a drying box at 60 ℃, and performing injection molding by using an injection molding machine to obtain four flame-retardant nylon resins (CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA).
And taking the obtained flame-retardant nylon resin for oxygen index test. The oxygen indices of CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA were 28.3%, 28.1%, 27.5% and 27.4%, respectively, as determined according to GB/T2406-2009.
Examples 41 to 44
Preparing a metal phenylphosphonate flame-retardant material:
(1) adding 1g of graphene oxide and 300mL of water into a reaction vessel, performing ultrasonic treatment at room temperature for 1h, stirring for 2h, then adding 2g of piperazine into the reaction vessel, and adding N2Condensing and refluxing for 6h at 100 ℃ in the atmosphere, filtering to obtain black precipitate, and drying in vacuum at 60 ℃ to obtain piperazine reduction modified graphene oxide (Pip-GO).
(2) Respectively adding 0.632g of phenylphosphonic acid, 50mL of water and 0.948g of Pip-GO into four reaction containers, stirring for 30min, then respectively adding 0.868g of cerium nitrate, 0.75g of aluminum nitrate, 0.439g of zinc acetate and 0.498g of cobalt acetate into the four reaction containers, stirring for 30min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 24h at 100 ℃, centrifugally washing with ethanol, and drying in vacuum at 60 ℃ to obtain the metal phenylphosphonate flame retardant material (CeHPP-PG, AlHPP-PG, CoHPP-PG and ZnHPP-PG).
Examples 45 to 48
Preparing flame-retardant nylon resin:
four parts of 20g of nylon resin were weighed, 1.05g (5 wt%) of the metal phenylphosphonate flame retardant material of examples 41 to 44 was added to each of the four parts of nylon resin, dried in a vacuum oven at 80 ℃ and melt-blended in a twin-screw extruder. The temperatures of the 3 sections of the extruder are set to be 220 ℃, 225 ℃ and 230 ℃ respectively. And (3) cooling the blend, cutting into granules, drying the granules in a drying box at 60 ℃, and performing injection molding by using an injection molding machine to obtain four flame-retardant nylon resins (CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA).
And taking the obtained flame-retardant nylon resin for oxygen index test. The oxygen indices of CeHPP-PG/PA, AlHPP-PG/PA, CoHPP-PG/PA and ZnHPP-PG/PA were determined to be 30.1%, 29.9%, 28.3% and 28.2% respectively according to GB/T2406-2009.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. The metal phenylphosphonate flame-retardant material with adjustable morphology is characterized by having the following structural formula:
wherein M isn+Is Ce3+、Al3+、Zn2+Or Co2+。
2. The shape-controllable metal phenylphosphonate flame-retardant material as claimed in claim 1, wherein: including lamellar and rod-like morphologies; when the coordinated metal ion is Ce3+、Al3+When the flame-retardant material is in a sheet-layer shape, the metal phenylphosphonate flame-retardant material is prepared by the following steps of (1) preparing a flame-retardant material; when the coordinated metal ion is Zn2+、Co2+When the flame-retardant material is used, the flame-retardant material is in a rod shape.
3. Morphology ofThe preparation method of the adjustable metal phenylphosphonate flame retardant material is characterized by comprising the following steps: piperazine and graphene oxide are reacted to obtain piperazine reduction modified graphene oxide, and phenylphosphonic acid is coordinated with metal ions and reacts with the modified graphene oxide to obtain a metal phenylphosphonate flame retardant material; wherein the metal ion is Ce3+、Al3+、Zn2+Or Co2+The method is used for adjusting the appearance of the metal phenylphosphonate flame-retardant material.
4. The preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 3, wherein the reaction route is as follows:
5. the preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 3, characterized by comprising the following steps:
(1) mixing graphene oxide with water, performing ultrasonic treatment for 1 hour at room temperature, stirring for 1-4 hours, adding piperazine, and adding N2Condensing and refluxing for 4-8 h at 80-120 ℃ in the atmosphere, filtering to obtain black precipitate, and performing vacuum drying at 50-100 ℃ to obtain piperazine reduction modified graphene oxide which is marked as Pip-GO;
(2) mixing phenylphosphonic acid, water and Pip-GO, stirring for 20-40 min, adding metal salt, stirring for 20-40 min, reacting the reaction solution at 80-120 ℃ for 18-30 h, centrifugally washing with ethanol, and vacuum drying at 50-100 ℃ to obtain a product, namely the metal phenylphosphonate flame retardant material, which is marked as MHPP-PG.
6. The preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 5, wherein the preparation method comprises the following steps: the mass ratio of the graphene oxide to the water to the piperazine is 1: 0.2-0.8: 1 to 5.
7. The preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 5, wherein the preparation method comprises the following steps: the metal salt is one of cerium nitrate, aluminum nitrate, zinc acetate and cobalt acetate.
8. The preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 5, wherein the preparation method comprises the following steps: the mass ratio of the phenylphosphonic acid to the water to the Pip-GO is 1: 0.05-0.15: 1 to 2.
9. The preparation method of the metal phenylphosphonate flame-retardant material with controllable morphology as claimed in claim 5, wherein the preparation method comprises the following steps: the molar ratio of the phenylphosphonic acid to the metal salt is 1: 1.5 to 2.5.
10. The application of the metal phenylphosphonate flame-retardant material with adjustable morphology in the preparation of a high-molecular flame-retardant material is characterized in that: the metal phenyl phosphonate flame retardant material accounts for 1-10 wt% of the high polymer flame retardant material.
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